Plaster of paris bandages to make casts of improved strength,water-resistance and physiological properties

ABSTRACT

MINOR ADDITIONS OF POLYVINYL PYRROLIDONE AND MELAMINE-FORMALDEHYDE RESINS TO PLASTER OF PARIS BANDAGES PERMIT MAKING &#34;CASTS&#34; OF IMPROVED STRENGTH AND WATERRESISTANCE WITH GOOD PHYSIOLOGICAL PROPERTIES.

United States Patent O US. Cl. 106-116 7 Claims ABSTRACT OF THE DISCLOSURE Minor additions of polyvinyl pyrrolidone and melamine-formaldehyde resins to plaster of Paris bandages permit making casts of improved strength and waterresistance with good physiological properties.

In my copending application entitled Plaster of Paris Bandages to Make Water-Resistant Casts, Ser. No. 65,732, filed Aug. 20, 1970, of which this application is a continuation-in-part, I have discolsed the use of polyvinyl pyrrolidone in plaster of Paris bandages to improve the water-resistance of casts made therefrom. I have now discovered practical and economical means of further improving the properties of casts not only in respect of strength and water-resistance but also in physiological acceptability. It has been known (see U.S. Pats. Nos. 2,842,120 by Foglia, Smith and Detwiler and 2,842,138 by Billings, Brickman and Eberl) that certain melamine-formaldehyde (triazene-aldehyde) resins (see US. Pats. Nos. 2,260,239 by Talbot and 2,310,004 by Widmer et al.) can be used to greatly increase strength and water-resistance of casts. However, use of such casts is subject to irritating and/or allergic reactions on the skin of both patients and cast-room personnel. Some persons are sensitive to the traces of formaldehyde always present in uncured such resins, or if not initially they may become sensitized by repeated use of the product. Furthermore, there is another type of reaction even more serious, that sometimes develops on the hands of the surgeon or cast-room technician who uses the product repeatedlya reaction that may be related to the amino groups in the resin. In spite of the very desirable strength and water-resistant properties of such casts, these reactions have markedly restricted their use. It may be further pointed out that recently plaster of Paris bandages have been used to make an interesting and extensive variety of art objects. Since such items are sometimes highly valued and may be kept or sold as, of more or less permanent value, it is highly desirable that such objects have great strength, permanence and resistance to moisture and deteriorating action of molds and other organisms-that this type of cast gives. While my first-mentioned disclosure shows water-resistance casts, I have now been able to improve on my earlier results in respect to strength and water-resistance and at the same time ameliorate any problems due to irritative or allergenic properties. As is well recognized by allergists and dermatologists, there are certain individuals that are sensitive or may be sensitized to a wide variety of even apparently innocuous materials, so that one does not claim to completely eliminate allergic or other skin reactions from all individuals, but herein are disclosed means of greatly reducing such problems as may exist in the use of these casts.

Specific embodiments of my invention will be illustrated in the following examples and certain modifications and extensions will be described hereinafter while others will be evident to those skilled in the art. All proportions are by weight unless otherwise noted.

Patented June 20, 1972 EXAMPLE 1 81 parts of high-density, low-consistency (see U.S. Gypsum Co. bulletin I.G.L. No. 19 for methods of testing plaster) plaster of Paris made by steam-calcining gypsum (see US. Pat. 1,901,051, issued Mar. 14, 1933 to Randel and Dailey) is slurried in 36 parts of a liquid comprising 80% toluene and 20% monomethyl ether of ethylene glycol in which is mixed 10 parts uncured melamine-formaldehyde resin prepared with a mol ratio of melamine to formaldehyde of 1:2, and 10 parts of dry polyvinyl pyrrolidone of average molecular weight 40,000. To the slurry was then added 0.4 part powdered potassium sulfate, 1.06 parts powdered potassium chloride, 1 part powdered ammonium sulfate and 1 part water-insoluble polyvinyl acetate (as used in US. Pat. No. 2,655,148). The mix was well stirred until all soluble materials dissolved and the resin softened. The resulting slurry was then coated on 32 x 28 mesh surgical gauze to form a discontinuous coating and dried at 200 to 230 F. for 10 minutes to yield a dry product weighing 210 to 240 grams per 5 square feet. The product was slit into 4 inch by 5 yard strips, rolled into a bandage and packaged in aluminum foil or polyethylidene (Saran) sheet in order to protect it from atmospheric moisture. When tested by the methods of Federal Specification GG'B-10ld, the bandage showed a settingtime of 5 minutes and low loss of plaster both dry and when wet and squeezed out to make a cast. A cast made from a 4 x 5 bandage gave a strength about 200 lbs. greater than an ordinary cast after 1 days drying and broke as a unit exhibiting a structure in which plaster is bonded to itself and to the backing, in contrast to an ordinary cast that shows little or no bonding to the backing. Repeated use of these bandages did not result in skin reactions. When a cast was dried for 3 days and then soaked in water for 24 hours it retained 95% of the strength of a cast 4 days old and not soaked in water. An ordinary cast in this test would retain only 50 to 60% of its strength.

EXAMPLE 2 276 grams of the dry, uncured resin and 75 grams of the polyvinylpyrrolidone of Example 1 were placed into a wide-mouthed glass jar with a tight, screwed-on cover (for example, rubber-gasketed). 15 grams of ammonium chloride (polymerization or condensation catalyst for the resin) were placed in a tightly sealed or tightly wrapped water-soluble film packet (for example water-soluble polyvinyl alcohol film) so as to keep it out of contact with the resin and prevent polymerization of the resin in storage. The packaging was done in a dry atmosphere in order to prevent absorption of moisture by the resin and the polyvinylpyrrolidone, and the jar was kept tightly sealed until its contents were used. When ready to use the contents of the jar were dumped into a container of a size to permit complete immersion of the bandage to be used and a jarfull (1 pint) of tepid water was added and the mix stirred until dissolved. A 4 inch x 5 yd. ordinary bandage (a fast-setting bandage made by the methods, for example, of US. Pats. Nos. 3,191,597;

' 3,282,265; 3,236,232; 3,294,087 or 2,557,083), the excess solution squeezed out (for example, leaving about 35% of the weight of the dry bandage of solution) and a cast made according to the above-noted Federal Specification. The set was about 5 min. and the cast wassimilar in properties to the cast of Example 1. If the cast is available in a polyethylene envelope, the solution may be poured into the envelope in amount sufi'icient to wet it thoroughly and the excess returned to its container. If used economically this amount of solution is suflicient to wet about 9 4-inch x 5-yd. or 20 3-inch x 3-yd. bandages. The above procedure makes over 1% pints of solution which can be used for up to about 2 hours. Repeated use of this solution failed to elicit any skin reactions.

EXAMPLE 3 parts of the resin and 5 parts of the polyvinylpyrrolidone of Example 1 were dissolved in 35 parts water containing 0.4 part boric acid, 1.5 part aqueous ammonia (29.4% NHg), 1.6 part water emulsion containing 55% water-insoluble polyvinyl acetate (softening-point 200 to 250 F.) and 1.2 part ammonium sulfate. Into this solution were slurried 85 parts of the plaster of Paris of Example 1. The slurry was coated as before on 32 x 28 mesh surgical gauze but dried for about 30 minutes in a circulating-air oven at about 115 F. In this case, where the resin is in aqueous solution with a catalyst, the drying must be done at low temperature so as to prevent s u bstantial polymerization of the resin and the final product must be completely dry and kept so in order to prevent polymerization of resin in storage. Casts made from .the product gave good strength and water-resistance and repeated use elicited no skin reactions.

EXAMPLE 4 A slurry was made as in Example 3 except that the ammonium sulfate was omitted from the slurry and the coated gauze could be dried for about 5 minutes at about 230 F. The dry bandage was sprinkled on one surface with a thick slurry of ammonium chloride in melted polyethylene glycol of 1500 average molecular-weight and melting-point 40 C. in proportion to give ammonium chloride in the amount of 12% of the weight of resinthe slurry being deposited in the form of separate, small droplets. Cast made with the product were similar to those of Example 1 and no skin reactions were encountered. A methoxy-polyethylene glycol of similar M.P. can be used in place of the polyethylene glycol.

EXAMPLE 5 A solution was made up containing 102 parts of the resin, 13 parts of the polyvinyl acetate emulsion and 50 parts of the polyvinylpyrrolidone of Example 3, 1.5 parts casein (Argentina acid) and 12 parts ammonium sulfate in 166 parts of the aqua ammonia of Example 3 and 202 water, 680 parts of the plaster of Paris of Example 1 was slurried with this solution after all soluble material was dissolved. The product was coated and dried as in Example 3 and results were similar to those of Example 1.

EXAMPLE 6 A solution was made up containing 27 parts of the resin, 3.6 parts of the polyvinyl acetate emulsion and 27 parts of the polyvinylpyrrolidone of Example 1 with 82 parts 29.4% aqua ammonia, 21 parts water, 3.6 parts potassium sulfate and 3.3 parts ammonium chloride. The solution was slurried with 180 parts of the plaster of Paris of Example 1 and coated and dried as in Example 3, with results similar to those of Example 1.

EXAMPLE 7 The procedure of Example 3 was repeated except that 0.8 part high molecular-weight dextran that softens in water but does not readily dissolve, was used in place of the polyvinyl acetate emulsion, as binding agent. This substitution was also made in the procedure of Example 4 with results similar to those of Example 1.

EXAMPLE 8 The procedures of Examples 5 and 6 were repeated using the dextran of Example 7 in place of the polyvinyl acetate emulsion in amount equal to the solids content of the emulsion. Results were similar to those of Example 7.

EXAMPLE 9 When the dextran of Example 7 was used as the sole binding agent in either a water-slurry or a slurry-liquid of water, methyl, ethyl or isopropyl alcohol or toluene or the slurry-liquid of Example 1, it is found that the cast made from such bandages (without polyvinylpyrrolidone or melamineformaldehyde resin) when dry weighs considerably more than a cast made from bandages of the ordinary type as made by any of the methods of the patents as cited in the above Example 2. It has not been determined exactly why this is but it may be suggested that the dextran combines with some of the excess water to fill up or lessen some of the voids in the cast as it drys and adds some weight with a corresponding increase in strength. Also it is found that the resulting dry cast is more hydrophobic (less water-absorbent) than an ordinary-type cast and thus more water-resistant.

In general all of the bandages of the above examples aged well at ordinary temperatures when Well dried and protected from moisture and they set in 4-5 minutes when wet preparatory to use in making a cast; they lost little plaster when handled dry and when wet and squeezed out to make a cast; casts made from them were strong, waterresistant and irritating and/ or allergenic properties were minimal.

The useful amounts of resin vary between 5 and 20% of the weight of plaster of Paris, with a preference for 10 to 15%. The polyvinylpyrrolidone is used in amounts from 10 to 150% of the weight of resin, with a preference for 50 to 100% Melamine-formaldehyde resins with mol ratio of melamine to formaldehyde from 1:15 to 1:1.33 or 121.5 to 1:25 can be used with a preference of the ratio 1:1.7 to 122.5. Plaster set-accelerator (potassium sulfate, ammonium sulfate or zinc sulfate) is used in amount from 0.5 to 2% K equivalent based on weight of plaster of paris. Resin polymerization catalyst (ammonium chloride, ammonium sulfate, zinc chloride or aluminum sulfate) is used in amount from 5 to 15% of the weight of resin in terms of NH Cl equivalent, but the optimum 1s 2 to 3.5 grams per 4-inch x 5-yd. bandage or from 210 to 240 grams of bandage. The solution of Example 2 should contain 2% of its weight of NH Cl equivalent but may vary from 1 to 5%. Ammonium sulfate is less active than ammonium chloride but gives better aging of the resin when in contact therewith. When non-aqueous slurry liquid is used one can use a mixtue of ammonium sulfate and potassium chloride which, when wet is the same as ammonium chloride and potassium sulfate, the former being a good polymerization catalyst and the latter a good plaster set-accelerator, and the mix in contact with dry resin gives better stability. Similarly a mixture of zinc chloride and ammonium sulfate can be used.

Other non-aqueous slurry-liquids can be used such as methanol, ethanol, propanol, isopropanol or the monomethyl or monoethyl ether of ethylene glycol. It is desirable to use a liquid that at least softens if not dissolves the resin and, except in the case of the polyvinyl acetate dispersion (emulsion) the binder should dissolve or at least soften in the liquid. Dextran is useful in this regard since it softens in water, alcohols (as listed above) and also in hydrocarbons like toluene. As a matter of fact polyvinyl acetate functions well when dissolved or softened in a solvent, containing monomethyl or monoethyl ether of ethylene glycol, in which it is soluble or softenable, as used in Example 1. Of these monoethers one uses 10 to 30% in an inert, volatile liquid hydrocarbon. Or one can use 10 to 40% Water in one of the alcohols listed above, polyvinylpyrrolidone also is soluble inwater and the abovelisted monoethers and alcohols but not in hydrocarbons alone; however it is not necessary that it be dissolved in the slurry-liquid aside from the standpoint of uniformity of the slurry.

Thus the use of polyvinyl pyrrolidone minimizes the irritating and sensitizing properties of melamine-formaldehyde resins and other ingredients of plaster of Paris casts. Polyvinylpyrrolidone of average molecular-weight 40,000

is preferred although material in the range from 10,000 to 360,000 can be used.

In general I may use the procedures of the above-mentioned patents of Foglia et al. and Billings et al., except with the addition of polyvinylpyrrolidone as herein disclosed. Although I prefer the plaster of Paris described in my Example 1, I may also use low-density, high-consistency plaster of Paris that is made by calcining gypsum in a kiln. In order not to show a gritty feel, the plaster of paris should be at least as fine as to pass a 100 mesh U.S. Standard screen and the set-accelerator and catalyst should also be this fine. The resin, in order to dissolve quickly should have particles in the range of 1 to 25 microns in size. While there is some advantage from the standpoint of its bonding action, it is not necessary for the resin to dissolve in the slurry. A thorough mixture of finely-divided resin, plaster of Paris, polyvinylpyrrolidone and plaster set-accelerator will function as long as an adequate binder is present.

The water-soluble film as used in Example 2 can be 85 to 90% hydrolyzed polyvinyl acetate with a molecular-weight not over that indicated by its viscosity in 4% aqueous solution at 20 C. of 48 centipoises as determined by the Hoeppler falling-ball method. If the percent hydrolysis is as high as 98% the viscosity should not be over 6 cps. The package used in this example can be a glass or metal jar with a moisture-vapor-tight cover or it can be a water-vapor-proof envelope of plastic (polyethylidene chloride-Saran, aluminum or steel foil or thicker polyethylene, polypropylene, polyvinyl chloride or 99 to 100% hydrolyzed polyvinyl acetate of 60 to 70 cps. as above determined). If the jar is to be used to measure the water for the solution, it should hold 453 parts water for 276 parts resin. The packet of catalyst can, of course, be separated from the resin by any obvious means but it is very convenient to tightly wrap or seal it in a watersoluble film so that the Whole contents of the packaging including catalyst and its wrapper may be emptied out and dissolved in the water.

The binding-agent is used in from 0.5 to 1.5% of the weight of plaster of paris in the bandage and includes polyvinyl acetate emulsion, polyvinyl acetate dissolved in a solvent, dextran, dextrin, cooked starch or cold-waterinsoluble, hot-water-soluble polyvinyl alcohol (see US. Patent application, Ser. No. 42,446 by Smith). The starch is prepared by cooking at near the normal boiling-point in part or all of the Water to be used in the slurry. Dextrin is dissolved in hot water (ISO-212 F.). Polyvinyl alcohol is dissolved in hot water and the dextran is merely dissolved in the slurry-liquid (toluene, alcohol, mono-ether of ethylene glycol or water). Polyvinyl acetate emulsion or dextran is used in any of the formulations herein given the others are used in water slurry. Dextran is made by the action of certain enzymes on sucrose and the material of different solubilities is obtained by fractionation.

.As backing material normally 32 x 28 mesh surgical gauze is used but any flexible, porous, inert, preferably water-wetting material may be used. In order to increase the rate of wetting of a bandage-roll--and also to reduce dusting of the dry bandagethere may be used in the slurry 0.05 to 0.15% of the weight of plaster of Paris of a wetting-agent such as sodium lauryl sulfate or sodium alkyl naphthyl sulfonate; or 0.1 to 1%, preferably 0.5% of water-soluble polyethylene glycol (Carbowax), methyl cellulose, hydroxyethyl ethyl cellulose or hydroxypropyl methyl cellulose.

It should be emphasized that the melamine resin should be very dry and if the polyvinylpyrrolidone is to contact it in storage, it should likewise be very dry if good aging is to be had. In the mix as in Example 2, if the polyvinylpyrrolidone is not perfectly dry, it can be enclosed with the catalyst or added separately to the solution at the time of use. In addition to the catalysts mentioned other acidreacting materials such as zinc sulfate that will give a solution pH of 6 or below, will function.

With further respect to the action of polyvinylpyrrolidone in reducing irritating and sensitizing properties, I have discovered that even in amounts from 5 to 25% in soaps, shampoos and detergents it is effective; for example, in soaps used almost daily by surgeons in scrubbing their hands which become very sensitive and irritated and in shampoos which irritate the eyes. In respect to dextran, it is of course very acceptable physiologically, having been successfully used in solution in water in its more readily dispersible form as a blood volume extender. As a plaster of Paris bandage bonding-agent, as indicated, the less readily dispersible forms are effective in bonding the plaster as the bandage is wet, but the more readily dispersible forms, especially in combination with cooked starch and/or dextrin as used in water or aqueous ammonia slurries show acceptable bonding action and exhibit the above-mentioned increased weight, strength and water-resistance of casts.

Having thus described my invention, what I claim is:

1. A plaster of Paris bandage containing a major proportion of powdered plaster of Paris and a minor proportion of: (1) an uncured melamine-formaldehyde resin of molecular ratio melamine to formaldehyde of between 1:15 and 1:25, in amount from 5 to 20% of the weight of plaster; (2) polyvinyl pyrrolidone of molecular-weight between 10,000 and 360,000, in amount from 10 to of the weight resin; (3) a binding-agent in amount from 0.5 to 1.5% of the weight of plaster of Paris and selected from the class consisting of polyvinyl acetate, cooked starch, dextrin, water-insoluble, water-swellable dextran and cold-water-insoluble, hot-water-soluble polyvinyl alcohol; (4) a plaster of Paris set-accelerator in amount from 0.5 to 2% of the weight of plaster and selected from the class consisting of potassium sulfate, and zinc sulfate; (5) a resin polymerization catalyst in amount from 5 to 15% of the weight of resin and selected from the class consisting of ammonium chloride, ammonium sulfate, zinc chloride, aluminum sulfate, potassium chloride With ammonium sulfate, and mixtures of the herein listed catalysts.

2. The bandage of claim 1 wherein the said molecular ratio is 1:2, the said average molecular-weight of said polyvinyl pyrrolidone is 40,000, the said bonding-agent is polyvinyl acetate and the said plaster of Paris set-accelerator is potassium sulfate.

3. The bandage of claim 2 wherein the said catalyst is ammonium chloride.

4'. In a method of making a plaster of Paris bandage by mixing powdered plaster of Paris, a plaster of Paris set-accelerator, a bonding agent, an uncured melamineformaldehyde resin and a resin polymerization catalyst in a volatile, inert liquid; coating the mix upon a flexible, porous, inert backing material and heating the so-coated backing to evaporate the said liquid and adhere the coat ing; to said backing without decomposing the said ingredients: wherein the improvement comprises adding to said liquid, polyvinyl pyrrolidone of average molecular weight between 10,000 and 360,000 in amount from 10 to 150% of the weight of said resin.

5. The method of claim 4 wherein (l) the said set-accelerator is in amount from 0.5 to 2% of the weight of said plaster and is selected from the class consisting of potassium sulfate and zinc sulfate (2) the said bondingagent is in amount from 0.5 to 1.5 of the weight of said plaster and is selected from the class consisting of (a) polyvinyl acetate in the form of an emulsion in a volatile, inert liquid (b) polyvinyl acetate in the form of a solution in a volatile, inert solvent (c) cooked starch (d) dextrin (e) water-insoluble, water-swellable dextran and (f) cold-water-insoluble, hot-water-soluble polyvinyl alcohol (3) the said uncured melamine-formaldehyde resin has a mol ratio of melamine to formaldehyde of from 1:15 to 1:1.33 and is in amount from 5 to 20% of the weight of the said plaster (4) the said resin polymerization catalyst is in amount from 5 to 15 of the weight of said resin and is at least one catalyst selected from the class consisting of ammonium chloride, ammonium sulfate, zinc chloride, aluminum sulfate, potassium chloride with ammonium sulfate, and mixtures of the herein listed catalysts and (5) the said polyvinyl pyrrolidone has an average molecular-weight of about 40,000.

6. In a plaster of Paris bandage comprising (1) powdered plaster of Paris bonded to itself and to a backing material (2) a set accelerator and (3) uncured melamineformaldehyde resin in amount from 5 to 20% of the weight of plaster; the improvement resulting from the presence of an additional ingredient comprising from 10 to 150% of the weight of resin, of a polyvinylpyrrolidone of molecular-weight between 10,000 and 360,000.

7. The bandage of claim 6 wherein the said molecularweight is an average of 40,000.

References Cited 5 UNITED STATES PATENTS 2,557,083 6/1951 Eberl 106-1l 1 2,842,120 7/1958 Foglia et a1. 106-111 2,842,138 7/1958 Billings et al. 106-411 10 JAMES E. POER, Primary Examiner U.S. Cl. X.R. 

